Hardening paste for the polymerization of organic compounds



United States Patent Q HARDENING PASTE FOR THE POLYMERIZATION OF ORGANIC COMPOUNDS No Drawing. Application July 25, 1956 Serial No. 599,923

Claims priority, application Germany July 27, 1955 6 Claims. (Cl. 252 430) The present invention relates to improvements in hardening pastes for use in promoting the polymerization of polymerizable unsaturated organic compounds.

It is known that unsaturated organic compounds can be polymerized in the presence of organic peroxidic compounds and amines which also may contain one or more S groups. This procedure, for example, has been used for the polymerization of the unsaturated polyesters of the so-called casting resins. The catalytically acting redox system renders it possible to complete the polymerization in a relatively short time without addition of heat from an external source.

However, in the practical application of this procedure, it was found that polymerization is initiated as soon as the polymerizable substances are admixed with the catalysts, so that the mixtures only possess a very short potlife. It was therefore proposed to divide the mixture to be polymerized into two parts, one of which contained the peroxidic component of the redox system and the other the amine. Also in this instance difficulties were encountered partly through a low pot-life of the components and because of the complications in use.

It has also been proposed to produce substantially orcompletely water free pastes of organic peroxides by kneading a moist organic peroxide with a plasticizer to produce a coherent mass and removing the water which escapes. Such pastes or masses can be used as additions to the polymerizable compositions. In use, however, they do not avoid the difliculties encountered during the admixture of the amine. Consequently, attempts were made to disperse the peroxidic compounds andthe amines in a high boiling liquid which is as viscous as possible, such as, for example, a plasticizer, and to add this catalyst mixture to the polymerizable compound or mixture shortly before use. It was found, however, that it, in general, was not possible to keep mixtures of amines and peroxides dissolved or dispersed in a liquid without such catalyst components rapidly reacting with each other and at times with explosive violence. This result was to be expected, as it was known that tertiary amines and peroxides react With each other with extraordinary vigor (see, for example, Chemische Berichte, vol. 86, pages 1071-2, 1953). 7

According to the invention, it was discovered unexpectedly that these reactions do not occur when organic peroxides are mixed with secondary or tertiary amines which contain one or more S0 groups in on position to the nitrogen atom. The hardening pastes according to the invention therefore contain at least one organic peroxidic compound and at least one tertiary or secondary amine which contains one or more $0 groups in a position to the nitrogen atom dispersed in an inert liquid preferably of high viscosity. The hardening pastes-according to the invention can be prepared by conventional methods,

for example, by mixing, kneading or trituration on'rolls.

The hardening pastes according to the invention can be used with excellent results for the polymerization of the most varied organic polymerizable compounds or mixice 2 tures. They are especially well suited foruse in the polymerization of unsaturated polyester resins, which may also contain other components taking part in" the polymerization, such as, for example, styrene, acrylic and methacrylic acid esters and the like.

An advantage of the hardening pastes according to the invention is that an excellent uniform distribution of the catalyst components is achieved and that therefore they are easily worked into the substances or mixtures to be polymerized.

In order to be able to produce and work up the hardening pastes according to the invention in an easyand simple manner, it is advantageous to select liquids of high boiling point as the inert liquid. The usual pl'a'sticizers, such as, for example, dibutyl phthalate, dioctyl phthalate, tricresyl phosphate or silicones, have been found excellently suited as the inert liquids for the preparation of the hardening pastes according to the invention.

It was found that secondary or tertiary amines in which the S0 group is attached to an aromatic radical are particularly advantageous and long lived when used in the preparation of the hardening pastes according to the invention.

The hardening pastes according to the invention can also contain relatively small quantities of heavy metals or heavy metal compounds as activators in addition to the peroxidic compounds and the amines.

It is also advantageous to incorporate extremely finely divided oxides of metals in the hardening pastes according to the invention in order to prevent a phase separation. Such oxides are, for example, oxides, such as silica or aluminum oxide, having a particle size of below 25 m produced by the dec'ompositionof volatile metal or metalloid compounds, such as silicon tetrachloride or TABLEI a-sulfone-substituted amine Peroxide 1 (CnH5SO2OH2hNH Dichlorobeuzoylperoxide. 2 (OIIgCuHrSOrCIfihNH B enzoylperoxide. 3 (0H3oeH.so20I-12)2NH. Dichlorobenzoylperoxide. 4. (CH3C6H4SOgO 2)2NOH3 Benzoylperoxide.

(CH3C6II-1BO2CH2)2NOH3 Dichlorobenzoylperoxide. (CHaCeILSOgOHQzNCzHs Do; (CH3CuH SOzCH2)2NCH C H DO. (CH3CnH SOzCIgIzhNCzHQCoHg 1130. o. Do. HaCtH4SO2CH2)2NH Di-t-butyldiperphth'alate. 12 (OH3CuH4SOzOHmNH 1 part di t butyldipcrpnthalate 1 part dichlorobenzoyl-peroxide. 13.-. (CHaOeHrsozCl-IflzNlZ 1 part cumenehydroperoxide, 1 part dichlorobenzyolperoxide.

The following examples show the results obtained in various polymerization tests with various hardening pastes according to the invention.

, 7 Example] A number of hardening pastes according to the invention were tested at aconcentration level of 1.5%. 10 .g of a polymerizable composition consisting of styrene mixed with an unsaturated polyester resin (30% styrene and 70% of polyglycol maleate) containing 0.3% of an activator consisting of lit-phenylethyl-dibutylamino-acetic acid ethyl ester chloride-l-Sy Cu++ (as naphthenate) per gram of polymerizable composition were used. The hardening pastes were composed of 60% of the combination of the sulfo amine and/the peroxide indicated and 40% of dibutyl phthalate.

The following Table 2 gives the polymerization periods and the maximum temperatures achieved during polymerization.

TABLE 2 Poly- Maximerimum Catalyst combination zation tempertimein ature, minutes 1-.. (CaHSOQOHQ)2NH+dichlorobenzoylperoxide... 11 74 '2-' (CHaCaHqS02CH2)SNH-i-bQnZOyIDQTOXldG 18 80 3." (CH3G IdLSO2CH )2NOH +dichlorobenzoyh 18 '61 PBTOXl e. p 4..- (CH3C6H4SOZCHZ)2Nc2H4ofiHg-i'dichlol'obenr 74 zoylperoxide.

5--. (01QgHiSOzCHz)zNCH +dichlorobenzoylper- 28 65 I 0x1 e. 6 (B-Naphthyl-S020112)zNCH3+dichlorobenzoyL 1 14 75 peroxide.

Example 2 A further number of hardening pastes according to the invention were testedata concentration level of 2%. 10 g. of a polymerizable composition were used, consisting of styrene and an unsaturated polyester resin (30% of styrene and 70% of polyglycol maleate) containing 0.2% of an activator consisting of fi-phenylethyl-dibutylamine hydrochloride-F5 Cu++ per gram of polymerizable composition. The hardening pastes were composed of 60% of the catalyst combination indicated and 40% of dibutylphthalate.

The following Table 3 gives the polymerization periods and the maximum temperatures achieved during polyr'n'eri- Various polymerizable mixtures were tested with various hardening pastes according to the invention. Each of the polymerizable mixtures contained 0.1 to 1% of an activator consisting of betaine ester chloride-}-220*y Cu++ (as naphthenate) per gram of polymerizable mix-- ture.

Hardening Paste 1: 60% 0f 3 parts (OH OuHlSOi' OH )zNH+5 parts dichlorobenzoylperoxide in 40% of dibutyl phthalate.

4 The following Table 4 gives the polymerization periods and the maximum temperatures achieved during polymerization.

TABLE 4 Poly- Maxi- Percent merimum Polymerizable mixture (about 10 g.) hardening zation tempaste time in persminture, utes C 80% unsat. polyester of maleic acid anhydride ethyleneglycol 20% monomeric methacrylic acid methyl ester 1.5 paste 1... 6 unsat. polyester of maleie acid anydride+1.2-propanedi01+30% triallylcyanurate 4paste 2.... 10 c 50% monostyrene+3% acrylic acid+2% acrylonitrile+45% polystyrene 3 paste 1 210 60 Acrylic acid methyl ester.. 3 pasteL... 3 97% vinylacetate|-3% acrylic acid 3 paste 4.- 7%

1 At 80. Paste 1=3 parts (CH OuH4SOzOH2) NH+5 parts dichlorobenzolyperoxide.

Paste 2=1 par:i (CH3C6H4SO2OI'IQ2NHII. part dichlorobenzoylperoxi e.

Paste 3 2 parts (CH3O6H SO2CH hNH-i-I part dichlorobenzoylperoxide.

Paste 4=1tpart (CH CtH SO2CI-Iz)zNH+1 part di-t-butyldiperphthal- TABLE 5 Polymeri- Maxi- Halogen carrier (0.2% of the polymerizable zation mum mixture) time in temperarninutes ture, C

1- Pheylethyldibutylamine H01 19 84 2- Tricthylamineoxide H01 19 78 3. Tetraethylammoniumchloride 28 80 4. Benzyloxytriethylammoniumchloride 12 83 5 Triethylaminoaceticacidethylesterchloride 15 78 6. Betainehydrochloride 27 39 Example 5 A number of polymerization tests were also carried out with difierent hardening pastes and difierent activators. The polymerizable material was styrene mixed with an unsaturated polyester resin (30% styrene and 70% of polyglycol maleate).

The following Table 6 gives the results obtained.

TABLE 6 Hardening Paste 2: 60% of 3 parts (011 6 1 14802- CHmNH-Fs parts dichlorobenzoylpcroxidc in 40% of dibutyl phthalate.

Activator 2: 0.07% B amine HCl+0.3y (311 per g.

of polymerizable mixture.

Percent Min. Pqlym. Max. HvZl) HvZDO Min. Polym. Max. Hm H.100 of hardworkable time 0. 1 day 1 day" workable time 0. 1 day 1 day ness time time Comparison:

With 0.7%, hardener 1+activator zHm 1 day:-9.3.; Ham 1 day=11.e.

With 1.5

hardener t+aetivator 2H? 1 day=16.8; Hv 1 day=18.9.

mooo) after 1 delv -Wicket herdaea at 20 (2 a fitte 1 y-- Example 6 TABLE 7 Castable for. Min.

Maximum temperature, C.

Polymerization time in minutes Percent hardness I claim:

1. A substantially stable hardening paste having extended shelf life for use as a catalyst in the polymerization of unsaturated organic compounds comprising a catalytic mixture of at least one catalytic organic peroxidic compound and at least one amine of the formula wherein R is selected from the group consisting of hydrogen, aliphatic radicals and aliphatic radicals substituted with an aromatic radical, and R" is selected from the group consisting of aromatic radicals and aromatic radicals substituted with an aliphatic radical dispersed in an inert high boiling liquid plasticizer, the quantity of said catalytic mixture in said dispersion being about 2. The hardening paste according to claim 1 in which said inert liquid plasticizer is viscous.

3. The hardening paste according to claim 1 containing in addition a relatively small quantity of copper as anactivator.

4. A hardening paste according to claim 1 containing a finely divided solid inorganic oxide selected from the group consisting of silica and aluminum oxide.

5. The hardening paste according to claim 1 in which said inert liquid plasticizer is an ester of a dibasic acid.

6. The hardening paste according to claim 1 in which 20 said inert liquid plasticizer is a dialkyl phthalate.

References Cited in the file of this patent UNITED STATES PATENTS Great Britain Apr. 28, 1954 

1. A SUBSTANTIALLY STABLE HARDENING PASTE HAVING EXTENDED SHELF LIFE FOR USE AS A CATALYST IN THE POLYMERIZATION OF UNSATURATED ORGANIC COMPOUNDS COMPRISING A CATALYTIC MIXTURE OF AT LEAST ONE CATALYSTIC ORGANIC PEROXIDIC COMPOUND AND AT LEAST ONE AMINE OF THE FORMULA 